Parasiticides



Patented Jan. id, 2945 2,367,534 massmcmns Frank B. Sinith and John N. Hansen, Midland,. Mich, asslgnors to The Dow Chemical Company, Midland, Mich, a corporation of Michigan N o Drawing.

Application February 15, 1941, Serial No. 379,015

18 illalms, (ill. 167-41) This invention relates to parasiticides and particularly to insecticidal and fungicidal compositions in which the diaryl-guanidine and arylbiguanide salts of dinitrophenols are employedas active toxicants.

Many synthetic organic compounds have been suggested as substitutes for lead, arsenic and copper-containing inorganic compounds as currently employed in insecticidal and fungicidal compositions. Many of these synthetic toxicants are injurious to plants, toxic to humans, and incompatible with other insecticidal materials.

Phenols as a class have not been fouinfl entirely satisfactory, clue to their solubility in water and high volatility, whereby they are readily leac -d or vaporized away from plant surfaces. more, are frequently corrosive to the of humans and produce aqueous solutions which burn foliage adversely aiiect normal plant metabolism. Phenols containing one or compositions comprising the less Water-soluble of these products may he applied to growing foliage at lethal concentrations without causing plant injury to the extent previousl inherent in the use of free phenols and their more soluble Inetallie salts.

The diazyl-guanidine and aryl-oiguanide salts oi the dinitro-phenois are, for the most part, crystalline solids of low vole. ty, stable to light and air, and not appreciably affected by carbon 3 l These compound inay be prepared by tee ting a diaryl-guanidine or an aryl-oiguani'de a ire-phenol to form the addition salt. naction may he carried out by contacting 1 "ens of equiinolecular proportions of -eno and although any suitamounts of the reactants may be employed. ed amounts of the solvent are required if c is carried out at temperatures beween l9 323 6., as, for example, at the using emperature of the reaction mixture en benzene or benzene and ethyl alcohol are t we loyed.

oi the amine solution to l a solution of the dlnltro-phefiol, the insoluble addition salt of the dinltro-phenol generally begins to separate or precipitate out of the mixture. The reaction is complete within from 30 minutes to 1 hour after the reactants are combined. The reaction mixture can then be cooled and filtered to separate out the desired phenolate product, which maybe further purified by washing with a small amount of such solvents as benzene, chlorooenzone, and the like. When the addition salt does not precipitate from the solution, the desired product may be separated by evaporating ofi the reaction solvent. In either case, the phenolate derivative is air-dried to remove residual solvent prior to use.

While this invention. is concerned with parasiticide compositions comprising the diarylguanidine or aryl-biguanide salts of dinitro-phenols generally, it is particularly directed to compositions embodying the reaction product obtained by the addition of the foregoing amines to 2.4-dinitro-phenols. ZAl-dinitro-phenol compounds which have been found especially valuable as insecticidal and fungicidal toxicant's are those derived from the reaction of the diarylguanidines and aiyl-biguanides with phenols having the formula N0: a radical selected from the grim? cimsisting Of and, alkyl, cycloalkyl, anowherein 'X represents aralkyl. These compounds are high-melting crystalline solids which are yellow to orange-red incolcr. They have an extremely low solubility in water, generally below 0.25 gram per 100 milliliters at 25 c. This 10v) solubil ty of the salt compounds, coupled with their highmelting point, stability, and low vapor pressure, results in an extended residual toxicity against insect pests and reduced foliage injury for compositions in which they are employed as toxic difiicultly soluble,

inorganic insecticidal toxicants which heretofore have been considered incompatible with phenols and phenolates.

The physical characteristics of representative diaryl-guanidine and aryl-biguanidensalts of dinitro-phenols are set forth in thefollowing table:

the reactants dissolved in a suitable organic solvent and thereafter contacting the mixture with a solution of the second reactant to produce the desired compound in situ.

The diaryl-guanidine and aryl-biguanide addition salts may similarly be incorporated in .TABLE I Solubility in Melting grams Per pH of satu- Compound rpuint liflgggfjfl ratedsolutlon I Color Phenyl-blguanlde salt oi2.4-dinltro=pi'mibl 165% am 1.3 Yellow. Phcnyl-biguanide salt of 2.4-dlnltro-6-cyclohexylhenoi 183 0.013 1 6.6 Orange. Diphenyl-g'uanidlne salt of ZAiinitro-fi-methyl-p eno1. 150-! 0.156 6.8 Yellow. Diphenyl-guanidine salt 2.4-dinitro-8-eyelohelry1-phenol. 172-; 111066 6 3 Orange-red.

other diaryl-guanidine and aryl-biguanidesalts of dinitro-phenols which may be employed as imrasiticide rtoxicamtsms .herein.discl=osed-.;include the 'l addition -;compounds obtained by reacting =-.suclr. amines as; alpha-naphthylfibiguanide; xylylbiguanide, tolylebiguanide, achlcrophenylebigua- .snide, 'dixylylg g-uanidine, -lditolyl.-guanidine, --di-.-

- (ohlorophonyl) guanidine,-andldixenylaguanidine -with 2.6+dinitroyphencl, ..2.5.-..dinitro -phen0.l, 2$- ;dinitrolr-methyhphenol, .-2A-.-dinitro-6-n-hexyl ,phenol, l2.4edinitro-6-.phenyll-phenol, :QA-dinitro- Alinitro =5 'naphthylamino-phenol, 2l5-.-dinitro- 6- wclohexyl -phenol, .'.-2.4'-dinit11o-5=cyclohexylphevml, a2.6-sli:aitro=4-cyclohexyl-phenol, and ;the

The compounds set forth above mayllbecema D19yedgenerally'as toxicants in parasiticide preparation's. .They may be used as constituents of .e'ithersdusting or spraying compositions. :In such use theywmayc-be compounded with various inert .carrliers,..such as diatomaceous-earth, .bentonite, ,talc, .sulfur, .wood fiours, inorganic phosphates, and the like,-to.form dusts adaptedto .be applied .with standarddus in eq ipment. .If desired, such Iiustsmay be employed as concentrates and subseouently .diluted .with .additional. inert. carrier. or suspendedin water. orotherliquid. carrier. to. form sprays. 'The diaryl-guanldineland aryl-biguanide addition salts may also be mixed with various wetting, dispersing, and sticking agents to form concentrates adapted to be diluted to produce spray compositions in which the'phenoiate is present in any desired concentration.

In the preparation of concentrates, from about 5 to about 90 per centzby weight of the amine addition salt is commonly employed. .The con- :ecntnation :of ithe amine lsalt .-lspray cor -dust -.oompesitionsn on capplieationt to;,pia.nts.- is preter- --ably between about 0.01 and l 5,0 per :eent by weight. .The rcomposition time in 'svhioh .the "salt is employed and l the -.concentration thereof 'lin the finaLcompositiom are dependent ,the particular parasite, re. g. .insect .-or ill-mills. l to ,be controlled-land the, circumstances tunderwhiclnsuchl controlistocbelaccomplished. In .other ..embodiments .of ..the invention .the .unineadditionssaltsemay,heuemployedhincccm- .binationlwithhil emulsions. .Theymayalso .be arsed .1111 water ssuspension with or .without .an additional emulsifying. .wettins, ..or .disn'ersing a ent. .Where 'itlis .(desired. toiimbre nate solid carriers with. the. e'dditionjalt, thelcarrierlmay be introduced intojhe'salt reaction mixtureand the, phenolate .precipitated directly inarid .on Lthe carrier surfaces. An .alternate procedure .consists of first wettingthecarrier'withbneof other standard type insecticidal compositions 20 either as the sole toxic ingredient of such composition .or 1 in; combination with; such materials .as.-inorgan:ic =.-pigments, organictdyes, lead arsen- .late, pyrethrine,.rotenone, cryolite, zinc sulfide,

organic thiocyanates, sulfur, -.copper sprays,

aryloxy-alkylols, aryloxy-alkylrhalides, aryloxyalkoxynalkylshalides, etc.

.The-severalexamplesareillustrative with re- .-spect'to-. the particular compound, composition 4191 and concentratlomemployed but are not to be-oonstmed'1as.-limiti ng the-invention:

FExmu: 1

-.20 rparts. by weight .of-the-ldiphenyl-guanidine .salt of 2l4-ldinitro 6acyclohexyl-phenol and 80 35,rparts by weight-of -diatomaceous earth were ,ground together.in..a .ballmill-to an average particle .size of .-less uthant-fi .microns diameter. ..15;.pounds ofnthe groundcomposition was dis- ;persed'inJOOPgaIlonS-ofWater to -give a spray ..mixture-.comprising .3.-0 :pounds of lthe active toxicant. lThis spray was applied to potato foliage infested "with :Colorado .potato beetle larvae andlkilledei .percent at the organisms in ..2l.days. .ln eacomparativedetermination, acid lead. larsenate .at a econcentration. of 1'3 pounds in -.100 galJonSrkiIIed-SQ percentofzthe potatobeetle ilarvaelirnz days.

Planners? e0 i fl partsuby .welghtl eithe diph nybguanidine -sz'alt .of -ZA-LdinitmsGacyclohexylephenol and 10 lpartsmby weight .nr lsodiumlaurylssulfiate were ground .togethern'n na-lball millto form apara- -sitibideconcentrate. .A.dispersion.of 1.1 pounds '.of.this mixture. mil-O0 gallons of .water killed 100 ,per .centnf. ten caterpillarslin-zedays. .A similar control was .obtained with aaldispersionof .3 pounds of acid lead arsenate in IUD-gallons of water. ..'I'he .composition econtaining the amine no additionsalt waslfound tolbeesubstantially less injurious tmapple: foliage than was theccomposition contining-theacid leadarsenate.

[Against Coloradopotatobeetlelarvae this concentratel at .055 pound .per .100 .gallons gave a 6 control lofr9'l'l5lper-cent in.'2;days. .In.this .de-

.terminationLthecontroLcomposition .of..3 pounds of. acidleartarsenateper.llldgllonsgavea mortality or.59.a.per .cent oithecrganisms in 2' days. -Anaqueouscompositiomcontaining 11.55, pound .iy'motltheeoncentratemer 100 gallons gave a control 'winstl-adultlMexicanlbean.beetle: of per cent dl srcompared to a'c0ntrol=of..25 per cent iforuacld lead larsenatev at.3 -,pounds .per. 100 galons.

'fi-3 lpoundtot-the::concentrate..in.100 gallgnopi water was found to give a 100 per cent kill of cabbage worm larvae in 2 days, as compared to' an 80 per cent control when 3 pounds of acid lead arsenate per 100 gallons of spray material was employed.

A dispersion of 0.55 pound of the concentrate I in 100 gallons of water gave a control against adult red spider of 100 per cent and against young red spider of 99.3 per cent in 2 days. When this composition was applied to red spider eggs,

the eggs hatched but the young spiders were either dead at emergence or died immediately thereafter.

EXAMPLE 3 45 parts by weight of the diphenyl-guanidine salt of 2.4-dinitro-6-cyclohexyl-phenol, 45 parts of diatomaceous earth, and parts of sodium lauryl sulfate were ground together to form an insecticidal concentrate. 1.1 pounds of this miX ture was dispersed in 100 gallons of water to obtain a composition comprising 0.5 pound of the toxicant. I per cent of tent caterpillar larvae in 2-3 days without'injury to apple foliage. trol of the larvae was obtained with 3 pounds of acid lead arsenate in 100 gallons of water.

EXAMPLE 4 A saturated water solution of the diphenylguanidine salt of 2.4-dinitro-6-cyclohexyl-phenol This dilute spray material killed 100 A similar conwas modified by the addition of sodium lauryl sulfate in the amount of 0.5 pound per 100 galions of solution. The resulting spray composition gave a 100 per cent control against adult red spiders in 3 days.

EXAMPLE 5 26' parts by weight of the diphenyl-guanidin EXAMPLE, 6

In a similar manner parts by weight of the phenyl-biguanide salt of 2.4-dinitro-phenol was ground with 80 parts by weight of diatomaceous earth. A dispersion of 2.5 pounds of this mix= ture in 100 gallons of water gave a kill against Colorado potato beetle larvae of 48.8 per cent'in 2 days.

EXAMPLE 7 arsenate at 3 pounds per 100 gallons kll1ed 80 per cent in 2 days and 100 per cent in 3 days.

Adilute aqueous composition comprising 0.55 pound of the amine salt concentrate gave a kill against Colorado potato beetle larvae of 100 per cent in 3 days. Against Mexican bean beetle larvae'this compositio killed 70 per cent in 3 days with but 20 per cent feeding, compared to Q a kill for acid lead arsenate at 3 pounds to 100 gallons of per cent in 3 days with 70 per cent feeding. Against poplar aphis the amine salt dispersion killed 98 per cent in-3 days; and against Aphis rumz'cis, 96.2 per cent in 2 days.

EXAMPLE 9 parts by weight of phenyl-biguanide salt of 2.4,-dinitro-6-cyc1ohexyl-phenol, 45 parts of diatomaceous earth,'and 10 parts of sodium lauryl sulfate were ground together to an average particle size of less than'5 microns. When 2.2 pounds of this concentrate was dispersed in 100 gallons of water, a composition was obtained giving a kill of 100 per cent against tent caterpillar larvae in 2 days. A more dilute composition comprising 1.1 pounds of the mixture per 100 gallons gave a control against adult red spider of 93 per cent and. against young red spiders of 100 per cent in 2 days. Red spider eggs treated with this composition hatched but the young spiders were either dead on emergence or died soon thereafter.

EXAMPLE 10 0.5 pound of sodium lauryl sulfate was added to 100 gallons of a saturated water solution of the phenyl-biguanide salt of 2.4-dinitro-6-cyclohexyl-phenol. The resulting composition gave a 100 per cent kill against adult red spiders in 3 days.

EXAMPLE 11 Compositions comprising the diaryl-guanidine and aryl-biguanide salts of the dinitro-phenols as toxic ingredients'and adapted to be employed in dusting operations are illustrated by the fol- 20 parts by weight of the phenyl-biguanide salt of 2.4-dlnitro-fi-cyclohexyl-phenol was ground with 80 parts of diatomaceous earth substantially as described above. The resulting composition at 15 pounds per 100 gallons gave a 99 per cent control of Colorado potato beetle larvae in 2 days. A composition comprising 3 pounds of acid lead arsenate per 100 gallons gave a control of 659 per cent of the potato beetle larvae in 2 days.

EXAMkLE 8 98 parts icy weight of the phenyl blguanide salt or 2.4l-dinltro-d-cyclohexyl-phenol and 10 parts of sodium lauryl sulfate were ground to gether to an average particle size of less than a microns. At 1.1 pounds per 100 gallons this com position gave a control against tent caterpillar larvae of ice per cent in 2 days. Acid lead lowing compositions.

Composition 1 Parts by weight Dixylyl-guanldine salt of ZA-dinitro-phenoL- 1 Sulfur 99 Composition 2 Diphenyl-guanidine salt of" 2.4 dinitro 6- methyl-phenol 2 Walnut shell flour 98 Composition 3- Parts by weight "Tolyl-biguanide salt of 2.4-dinitro-6-nhexyl-phenol 2.5

Diatomaceous earth 97.5%.

Composition 4 hexyl-phenol Petroleum oil 1.5 Bentonite 96.5

The above and related compositions may be applied with standard dusting equipment for the control of codling moth, red spider, thrips, and

' other parasites. 'Also, they may be dispersed in water in amounts of from 0 25 pound to 50 pounds per 100 gallons to form aqueous suspensions sult= able for application to the trunks and branches of trees during the dormant period or for spray- Parts by weight Parts by weight Phenyl-biguanide salt of 2.4-dinitro-6-cycloing the ground adjacentto trees or shrubs. When applied in this manner the aminesalts serve as active toxicants not only for the control of insect pests but also for the control of various spore-forming fungi. In such dilute form the compositions may be used with any suitable emulmercury, cyanide, fluorine, copper, etc. Numerous instances in which the amine salts have beencontacted with the skin of humans indicate that they are relatively non-corrosive and not inclined to produce dermatitis, even on repeated application.

A copending application Serial No. 378,972, filed concurrently herewith now United States Patent No. 2,304,821 sets forth the preparation ,and physical characteristics of a number of diaryl-guanidine and aryl-biguanide salts of dinitro-phenols and claims these addition salts as new compounds.

Other modes of applying the principle of our .invention may be employed instead of those explained, change being made as regards the materials and amounts concerned, provided the ingredients stated by any of the following claims or their equivalent be employed.

We therefore particularly point out and distinctly claim as our invention:

1. An insecticidal and fungicidal composition comprising as a toxic ingredient a compound selected from the class consisting of the diarylguanidine and aryl-biguanide salts of dinitrophenols in intimate mixture with a carrier.

"2. An insecticidal composition comprising as a toxic ingredient a compound selected from the group consisting of the diaryl-guanidine and.

aryl-biguanide salts of dinitro-phenols in intimate mixture with a finely-divided solid carrier.

3. An insecticidal and fungicidal spray comprising an aqueous dispersion of a finely-divided compound selected from the class consisting of .the diaryl-guanidine and aryl-biguanide salts of dinitro-phenols.

4. An insecticidal and fungicidal composition comprising as a toxic ingredient a diaryl-guanidine salt of a 2.4 dinitrol-phenol in intimate mixture with a carrier.

5. An insecticidal and fungicidal composition comprisingas a toxic ingredient a diaryl-guani- -.dine salt of a phenol having the formula comprising-as a toxic ingredient the diphenyiguanidine salt of a phenol having the formula wherein X represents a,radical selected from the group consisting of aryl, alkyl, cycloalkyl, and aralkyl in intimate mixture with a carrier.

8. An insecticidal and fungicidal composition comprising as a. toxic ingredient the diphenylguanidine salt of 2.4-dinitro-6-methyl-phenol in intimate mixture with a carrier.

9. An insecticidal and fungicidal composition comprising as a toxic ingredient the diphenylguanidine salt of 2.4-dinitro-6-cyclohexyl-phcnol in intimate mixture with a carrier.

10. An insecticidal and fungicidal composition comprising as a toxic ingredient an aryl-biguanide salt of a 2.4-dinitro-pbeno1 in intimate mixture with a carrier.

11. An insecticidal and fungicidal composition comprising as a toxic ingredient an aryl-biguanide salt of a phenol having the formula aralkyl in intimate mixture with a carrier.

12. An insecticidal and fungicidal composition comprising as atoxic ingredient a phenyl-bi-' guanide salt of a 2.4-dinitr0-phen'o1 in intimate mixture with a carrier.

13. An insecticidal and fungicidal composition comprising as a toxic ingredient a phenyl-biguanide salt of a phenol having the formula wherein)! represents a. radical selected from the group consisting of aryl, alkyl, cycloalkyl, and aralkyl in intimate mixture with a carrier. 7

14. An insecticidal and fungicidal composition comprising as a toxic ingredient the phenyl-bi guanide salt of 2.4-dinitr0-6-cyclohexyl-phenol in intimate mixture with a carrier.

15. An insecticidal composition comprising as a toxic ingredient a diphenyl-guanidine salt of a phenol having the formula wherein X represents a radical selected from-the group consisting of aryl, alkyl, cycloalkyl, and aralkyl, in intimate mixture with a finely-divided solid carrier.

16. An insecticidal composition comprising as a wherein X represents a radical selected from the toxic ingredient a, diaryl-guanidinesslt diludinitrb-G-cycio-hexyl-phenol in intimote mixture with a finely-divided solid carriergi?" 17.'An insecticidal composition comprising as phenol having the: formula a toxic ingredient a phenyl-biguanide salt of a group consisting of aryl, alkyl, cycloalkyl, and aralkyl, in intimate mixture with a finely-divided carrier.

18. An insecticidal composition comprising as a toxic ingredient an aryl-biguanide salt of 2.4- 

